DE2263963A1 - Polyvinyloxysuccinic acids - useful as complexing agents for alkaline earth ions, in compsns. for cleaning solid and metal surfaces, washing textiles and dishes - Google Patents

Abstract

Polyvinyloxysuccinic acid (I) consisting mainly of units of formulae (-CH2-CH(-OCH(COOH)-CH2(COOH)-)n (Ia) and (-A-) 100-n (Ib) (where -A- denotes the monomer unit of a polymerisable hydrocarbon, ether, ester or a mono- or dicarboxylic acid and esp. the ethylene, propylene, 1,1-dimethylethylene, phenylethylene, methoxyethylene, acetoxyethylene, carboxyethylene or 1,2-dicarboxyethylene gp.; units (Ia) and (Ib) may be arranged in opt. sequence; n is >=30 mol% of copolymer; av. D.P. is 3-100 esp. 5-50) are complexing agents for alkaline earth ions, esp. in washing, rinsing and cleaning compsns., present at pastes, dispersions or solns., contg. 5-95 wt.% (I) and 95-5% standard additives. Pref. (I) contain only (Ia) units. Pref. (I) are prepd. by (i) reacting a vinyloxysuccinate of a lower monohydric alcohol, esp. the Me ester, alone or with a co-monomer (A) in an inert solvent at 0 to -100 (-30 to -80) degrees C, with catalytic amounts of a Lewis acid, esp. with BF3 - etherate; saponifying prod. and opt. separating as the alkali salts.

Description

"Polyvinyloxysuccinic acids" The effect of detergents, dishwashing detergents and cleaning agents is based to a substantial extent on the presence of inorganic or organic substances Complexing agent for alkaline earths. Such complexing agents include, for example sodium tripolyphosphate or various organic complexing agents of the type Phosphonates or the aminopolycarboxylic acids. You have these phosphorus or nitrogen containing Complexing agents in connection with issues of environmental protection and criticized them blamed for the eutrophication of surface waters. Because of these Criticism sees the expert faced with the task of finding new complexing agents for Develop detergents, dishwashing detergents and cleaning agents that contain no phosphorus and nitrogen atoms contain.

The invention relates to polyvinyloxysuccinic acids, a method for their production and their use as complexing agents for alkaline earth ions, especially in detergents, dishwashing detergents and cleaning agents.

The polyvinyloxysuccinic acids essentially consist of units of the formulas Ia and Ib in which -A- the monomer unit of a polymerizable hydrocarbon, ether, ester or a mono- or dicarboxylic acid and preferably the ethylene, propylene, 1, 1-dimethylethylene, phenylethylene> methoxyethylene, acetoxyethylene, carboxyethylene or the 1 , 2-Dicarboxyäthylenrest, where the units of the formulas Ia and Ib can be arranged in any order, and n is at least 30 mol% of the copolymer, and the average degree of polymerization between 3 and 100, preferably between 5 and 50 is.

The new fabrics are preferred according to one of D.D. Coffman, G.H. Calf and A.B. Ness in "Journal of Organic Chemistry", 13, 223-226 (1948) for the Preparation of the polyvinyloxyacetic acid method described.

The process for making the compounds of the invention is characterized in that a vinyloxysuccinic acid ester of a lower monohydric alcohol, preferably the methyl ester, alone or with a comonomer A, preferably with ethylene, propylene, isobutylene, styrene, methyl vinyl ether, vinyl acetate, Acrylic acid, maleic anhydride, in an inert solvent at a temperature from 0 ° C to -100 ° C, preferably from -30 to -80 0C with catalytic amounts of a Lewis acid, preferably polymerized with boron trifluoride etherate and after peeling off of the solvent saponified.

The substances according to the invention are expediently in the form their alkali salts isolated. Optionally, the free carboxylic acids from the Salts are obtained, for example by having the saponification solution with Treated a cation exchanger and then concentrated under reduced pressure.

The new polyvinyloxysuccinic acids and their water-soluble salts are good complexing agents for alkaline earth ions.

They can be used with good success in place of the well-known phosphorus and nitrogenous ones Use complexing agents for a wide variety of cleaning tasks. Particularly preferred are the polyvinyloxysuccinic acids, which are composed entirely of units of the formula Ia exist.

The following are the compounds according to the invention with units of the formulas la or the formulas Ia and Ib and their water-soluble salts, in particular the alkali salts, known as polyvinyl oxysuccinates (PVOS).

The invention further relates to detergents, dishwashing detergents and cleaning agents, which are in solid form, as pastes, dispersions or solutions that have a Have content of complexing agents for alkaline earth metal ions, and those on the water- and / or solvent-free products are composed as follows: 5 - 95% by weight of the polyvinyl oxysuccinates, and 95-5% by weight of other conventional additives of detergents, dishwashing detergents and cleaning agents, especially organic or inorganic substances with a cleaning effect, preferably phosphorus and nitrogen-free substances.

If the agents according to the invention are of a solid nature, they lie they usually come in the form of fine to granular powders, agglomerates or granules. Such Agents can be practically anhydrous; but they can also be crystal water or water of hydration contain. The agents according to the invention can, however, also be used as pastes or dispersions or solutions are used; they then contain lesser or greater amounts of liquid solvents such as water or organic water-soluble solvents, in which the other components are partially or completely dissolved. For certain Cleaning purposes can be s.B. Use solutions up to 1 wt., Preferably contain up to 4% by weight of the solid agent. The solutions, dispersions or pastes can also be much more concentrated, so that the amount of solvent up to 30% by weight, preferably up to 50% by weight. In the solutions, dispersions or pastes, hydrotropes can also be incorporated.

The composition of the preparations according to the invention can, depending on their Application area can be very different. For the industrial cleaning of surfaces Solid materials with the exception of textiles, for example, are suitable products the following composition: 5 - 30% by weight polyvinyl oxysuccinate, 10 - 95% by weight phosphorus-free, substances from the group of alkali silicates and alkali carbonates with a cleaning effect and the caustic alkalis, 0-10% by weight surfactants.

These agents can also contain alkaline or neutral salts, Corrosion inhibitors, disinfectants, complexing agents, especially those for heavy metals, and other common ingredients of such agents. Suitable cleaning agents for the manufacturing sector of the metal industry are, for example Products of the following composition :.

10-30% by weight of polyvinyl oxysuccinate, 10-30% by weight of alkali metal silicates, 10-40% by weight of caustic alkalis, 0-10% by weight surfactants.

Preparations from are suitable as cleaners for the food industry the following composition: 5 - 30% by weight polyvinyl oxysuccinates, 10 - 20% by weight alkali silicates, 40-80% by weight of caustic alkalis, 0-5% by weight of surfactants.

As a cleaning agent for machine dishwashing in commercial and household dishwashers are preparations of the following composition usable: 5 - 90 wt .-% polyvinyl oxysuccinates, 95 - 5 wt .-% alkali silicates, 0 - 20 wt .-% alkali hydroxides or alkali carbonates, 0-10 wt .-% low-foaming nonionic surfactants, 0-25% by weight of other common ingredients in dishwashing detergents such as active chlorine compounds, enzymes, complexing agents for heavy metals, color and fragrances.

While the caustic alkali-containing preparations mostly only for cleaning Surfaces of solid materials in industry or in commercial operations and are used for machine dishwashing, are used as household cleaners or as a laundry detergent for soaking, washing and bleaching in industry, In commercial laundries or in the household, caustic alkali-free agents, their 1% aqueous solutions have a pH value of at most 11.5.

The soaking according to the invention, containing the polyvinyl oxysuccinates, Prewash, mild detergents, detergents or bleaching agents can be removed from the use a wide variety of fibers of natural or synthetic origin. For this include, for example, cotton, regenerated cellulose or linen as well as textiles, the highly refined cotton or synthetic man-made fibers, such as polyamide, polyester, Contain polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers. The detergents according to the invention can also be used for washing the "easy-care", textiles made from synthetic fiber and cotton blended fabrics, sometimes also referred to as "non-iron" use.

The composition of this in 1% aqueous solution has a pH value of a maximum of 11.5 agents is in the range of the following recipe: O - 80, preferably 5-40% by weight of a surfactant component consisting of anionic and / or zwitterionic and / or nonionic surfactants, 5 - 95, preferably 10-80% by weight of polyvinyloxysuccinates serving as builder substances, 95-0, preferably 90 - 20% by weight of other inorganic and / or organic structural substances and, if necessary, a bleaching component, 0-30, preferably 1-25% by weight of other common ingredients of detergents and cleaning agents.

To the other usual detergent and cleaning agent ingredients include e.g. foam stabilizers, non-surfactant foam inhibitors, fabric softeners, Dirt carriers, brighteners, antimicrobials, enzymes, dyes and fragrances. The bleach component consists of bleaching active chlorine or active oxygen compounds and possibly Activators and / or stabilizers.

By using the polyvinyl oxysuccinates defined above, the do not contain phosphorus or nitrogen, the previously used or Phosphorus- and / or nitrogen-containing complexing agents proposed in the literature Partly or completely replace structural substances. When the condensed phosphates such as sodium tripolyphosphate and organic ones containing phosphorus and / or nitrogen Complexing agents in the usual commercial agents, e.g. half through the Polyvinyloxysuccinates and possibly by other common P- and / or N-free framework substances are replaced, then this leads to the application in the usual washing, rinsing and washing Cleaning liquors already lead to a considerable reduction in the P and / or N concentration in the sewage. Another advantage of the polyvinyl oxysuccinates is that they are stable to hydrolysis, in contrast to the tripolyphosphates, which are aqueous Solution can be split into the less effective orthophosphate.

The ability of the polyvinyl oxysuccinates to form complexes is at the Alkaline earths are particularly pronounced, so that they support washing and cleaning processes capital; on the other hand, their ability to form complexes for heavy metals - just like with other known complex-forming framework substances - only slightly. It recommends therefore, the agents according to the invention have low heavy metal complexing agents To add amounts of e.g. 0.1-5, preferably 0.1-2% by weight. As a complexing agent for heavy metals, especially for copper, ethylenediaminetetraacetic acid is suitable, for example, Diethylenetriaminepentaacetic acid or hydroxyethane diphosphonic acid or their salts.

In the detergents according to the invention, including in particular the advantages, Delicates and cooking detergents belong, the surfactant component preferably contains at least 50 percent by weight of anionic surfactants, with anionic surfactants essentially capillary-active sulfates and / or sulfonates and / or soaps are understood. the Amount of builders including polyvinyl oxysuccinates makes preferred 0.5 to 7 times and especially 1 to 5 times the total surfactant component the end. If the preparations according to the invention contain more than 40 percent by weight of surfactant component, then they are mostly used for commercial purposes, e.g. in laundries and in the textile industry used where they are used less alone, more often in combination with common additives will.

The composition of powdered preparations according to the invention that are used in particular as detergents or cleaning agents, is generally in the range of the following formulation: 5 - 50> preferably 8 - 40 wt., one surfactant component, consisting essentially of anionic and / or zwitterionic and / or nonionic Surfactants and optionally from one or more of the following substances: 0-10, preferably 0.5-8% by weight of foam stabilizers, 0-10, preferably 0.5 - 8% by weight of non-surfactant foam inhibitors, 95-5, preferably 92-10% by weight Polyvinyloxysuccinates, 0 - gO, preferably 5 - 82 wt .-% inorganic and / or other organic structural substances and, if applicable,

Bleaching components and O - 30> preferably 1 - 15% by weight others Detergent ingredients, such as dirt carriers, fabric softeners, antimicrobials, Enzymes, brighteners, dyes and fragrances, water.

The surfactant component is preferably at least 50% by weight from anionic surfactants from the group of alkylbenzenesulfonates, alkanesulfonates, Fatty acid ester sulphonates, olefin sulphonates, fatty alcohol or fatty alcohol glycol ether sulphates and the soaps. Foam-suppressed ones suitable for use in drum washing machines Detergents according to the above recipe contain either a combination Surfactants of the sulfonate and / or sulfate type and soap in a ratio of 30: 1 up to 1: 5, preferably 20: 1 to 1: 2, and / or a non-surfactant foam inhibitor. The foam suppression is particularly pronounced, the soap content at least 5 and preferably Contains at least 10% by weight of soaps of saturated fatty acids with 20-24 carbon atoms.

The bleaching component usually makes 5 - 40, preferably 7 - 35 wt. of all detergent.

The powdered detergents, dishwashing detergents and cleaning agents according to the invention can be produced by various methods known per se. So you can for example those in the form of a more or less fine powder or granules Mix the individual components together. After the technically preferred at the moment The production method for detergents, dishwashing detergents and cleaning agents is an aqueous approach the components that are insensitive to water and heat in a manner known per se, e.g.

dried on hot surfaces or in a stream of hot air.

The powder obtained are then further ingredients that are used in a such processing could lose their effect in whole or in part. These include e.g. foam inhibitors, bleaches, enzymes, antimicrobials, colorants and fragrances, etc. It may be advantageous, especially for gentle Incorporation of smaller amounts of substances by mixing them with a part to stir the structural substances first into a dry powdery preliminary product, which is then added to the washing powder, detergent or cleaning powder in the usual way will.

In the following, the washing, rinsing and washing machines according to the invention The ingredients contained in detergents are sorted by substance class described.

The surfactants contain at least one hydrophobic organic in the molecule Remainder and a water-solubilizing anionic, zwitterionic or nonionic Group. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 carbon atoms or around one alkyl aromatic radical with 6-18, preferably 8-16, aliphatic carbon atoms.

As anionic surfactants, e.g. soaps made from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids useful. Suitable synthetic anionic surfactants are those of the sulfonate type, Sulfates and the synthetic carboxylates.

As surfactants of the sulfonate type are alkylbenzenesulfonates (C915-alkyl), Mixtures of alkene and flydroxy alkane sulfonates and disulfonates, how to get them for example, from monoolefins with a terminal or internal double bond through Sulphonation with gaseous sulfur trioxide and subsequent alkaline or acidic Hydrolysis of the sulfonation products obtained into consideration. Alkanesulfonates are also suitable, that from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Further useful sulfonate-type surfactants are the esters of sulfo fatty acids, e.g. «-Sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or Sebum fatty acid.

Suitable surfactants of the sulfate type are the primary sulfuric acid monoesters Alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulphated fatty acid alkanolamides are also suitable, Fatty acid monoglycerides or reaction products of 1-4 mol of ethylene oxide with primary or secondary fatty alcohols or alkyl phenols.

Other suitable anionic surfactants are the fatty acid esters or -amides of hydroxy- or amino-carboxylic acids or -sulphonic acids, such as the fatty acid sarcosides, -glycolates, -lactates, -taurides or -isthionates.

The anionic surfactants can be in the form of their sodium, potassium and Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine are present.

Addition products of 4 to 40 are preferred as nonionic surfactants 4 - 20 moles of ethylene oxide in 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used. The addition products are particularly important from 5 - 16 mol of ethylene oxide to coconut or tallow fatty alcohols, to oleyl alcohol or secondary alcohols with 8-18, preferably 12-18 carbon atoms, as well as mono- or dialkylphenols with 6-14 lC atoms in the alkyl radicals. In addition to these water-soluble However, nonionics are also not or not completely water-soluble polyglycol ethers with 1 - 4 ethylene glycol ether residues in the molecule of interest, especially if they used together with water-soluble nonionic or anionic surfactants will.

Furthermore, the water-soluble, 20 - Containing 250 ethylene glycol ether groups and 10-100 propylene glycol ether groups Addition products of ethylene oxide to polypropylene glycol (= Pluron i cs), alkylenediamine-polypropylene glycol (= Tetronics R) and alkyl polypropylene glycols with 1 - 10 carbon atoms in the alkyl chain useful in which the polypropylene glycol chain acts as a hydrophobic residue.

There are also nonionic surfactants of the amine oxide or sulfoxide type usable.

The foaming power of the surfactants can be determined by a combination of suitable Increase or decrease types of surfactants; a reduction can also be achieved Achieve additions of non-surfactant organic substances.

Suitable foam stabilizers, especially in the case of sulfonate surfactants or sulfate type, capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylolamide type nonionics; in addition, fatty alcohols or higher are used for this purpose terminal diols have been proposed.

A reduced foaming power, which is desirable when working in machines is often achieved by combining different types of surfactants, e.g. from Sulphates and / or sulphonates with nonionics and / or with soaps. In the case of soaps, increases the foam damping with the degree of saturation and the carbon number of the fatty acid residue; So soaps made from saturated C20-24 fatty acids are particularly suitable as foam suppressors.

The non-surfactant foam inhibitors may include Chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mole of cyanuric chloride with 2-3 moles of a mono- and / or dialkylamine with 6-20, preferably 8-18 C atoms in the alkyl radical. Propoxylated and / or butoxylated act similarly Aminotriazines, e.g. products obtained by adding 5 - 10 moles of propylene oxide 1 mol of melamine and further addition of 10-50 mol of butylene oxide to this propylene oxide derivative receives.

Water-insoluble foam inhibitors are also suitable as non-surfactant-like foam inhibitors organic compounds such as paraffins or haloparaffins with melting points below from 100 ° C, aliphatic 018 to C40 ketones and aliphatic carboxylic acid esters, those in the acid or alcohol radical, optionally also in each of these two radicals, contain at least 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters); they can be used especially with combinations of surfactants of the sulfate and / or sulfonate type use with soaps to steam the foam.

Particularly low-foaming nonionics that are used both alone and used in combination with anionic, zwitterionic and nonionic surfactants and reduce the foaming power of high-foaming surfactants the addition products of propylene oxide to the capillary-active ones already mentioned Polyäthylengly'xoläther and the addition products also already described from ethylene oxide to polypropylene glycols and to alkylenediamine-polypropylene glycols or on Cl ~ 10-alkyl-polypropylene glycols.

As further builder substances, which in combination with the inventive Polyvinyloxysuccinates can be used, are weakly acidic, neutral or alkaline reacting alkali salts that precipitate or complex calcium ions to bind.

Suitable inorganic salts are in particular the alkali metal carbonates and bicarbonates as well as the alkali silicates, e.g.

Sodium silicates with a ratio of Na2O: SiO2 such as 1: 1 to 1: 3.5. The sulfates and borates of the alkalis can also be used.

Suitable organic salts include the non-capillary active, 1 - 8 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic acids, for example Alkali salts of benzene, toluene or xylene sulfonic acid, sulfobenzoic acid, sulfophthalic acid, Sulphacetic acid, sulphobuccinic acid or other sulphocarboxylic acids as well as the Salts of acetic acid or lactic acid.

Other suitable organic builder substances are the nitrogenous and phosphorus-free compounds of the type forming complex salts with calcium ions of the polycarboxylic acids or their salts, including polymers containing carboxyl groups counting. Citric acid, tartaric acid, benzene hexacarboxylic acid, carboxymethyl ether groups, for example, are suitable containing polycarboxylic acids such as diglycolic acid, 2,2'-oxydisuccinic acid as well as polyhydric alcohols partially or completely etherified with glycolic acid or hydroxycarboxylic acids, for example bis (0-carboxymethyl) ethylene glycol, mono- or bis (O-carboxymethyl) glyceric acid or carboxymethylated or oxidized polysaccharides. Also suitable are the polymeric carboxylic acids with a molecular weight of at least 350 of the type of polyacrylic acid, poly-ff-hydroxyacrylic acid, polymaleic acid, etc. and the salts of copolymers of maleic anhydride with ethylene, propylene or Vinyl methyl ether and the copolymerization of acrolein and acrylic acid in Correnwart of hydrogen peroxide and subsequent conversion according to Cannizzaro available Polyhydroxycarboxylic acids, Of the ingredients of the invention In particular, detergents and auxiliary agents are to be selected in such a way that that the preparations react neutrally to clearly alkaline; i.e. the pH of a 1% solution of the preparations should be in the range from 7 to 11.5. They give Fine and colored detergents usually have a neutral to slightly alkaline reaction (pH value = 7 - 9.5), while soaking, prewash and cooking detergents are somewhat more alkaline (pH value = 9.5 - 11.5) are set.

Dirt carriers can also be used in the preparations according to the invention be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. For this purpose, water-soluble colloids are usually used of an organic nature, such as glue, gelatin, salts of -thercarboxylic acids or ahersulfonic acids of starch or cellulose or salts of acid sulfuric acid esters cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and use other starch products than those mentioned above, such as degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

Soil-bearing properties also have those that are already non-ionic Surfactants described addition products of 1-4 moles of ethylene oxide with 1 mole of fatty alcohol with 8-18 0 atoms.

For the bleaching component, among those used as bleaching agents, In water H202 producing compounds the sodium perborate tetrahydrate (NaBO2 H202 3 3 H20) and monohydrate (NaBO2. H202) are of particular importance. But there are too Other borates that supply H2O2 can be used, e.g. the Perborax Na2B407 4 H202. These Compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxyhydrates, such as peroxycarbonates (Na2CO3. 1> 5 H202), peroxypyrophosphates, Citrate perhydrates, urea-H2O2 or melamine-H02 compounds as well as H202 delivering peracid salts, such as Caroate (KHSO5), perbenzoate or peroxyphthalate be replaced.

It is advisable to use the usual water-soluble and / or water-insoluble Stabilizers for the peroxy compounds together with them in amounts of 0.25 - to incorporate 10% by weight.

As water-insoluble stabilizers, e.g. 1 - 8, preferably Make up 2 - 7% of the weight of the entire preparation, they are mostly suitable Precipitation of magnesium silicates obtained from aqueous solutions MgO: 502 = 4 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1 other alkaline earth metal. Cadmium or tin silicate of the appropriate composition useful. Hydrous oxides of tin are also suitable as stabilizers. Water-soluble stabilizers that coexist with water-insoluble ones The organic complexing agents, the amount of which is 0.25-5, are preferred 0.5-2.5 of the weight of the entire preparation.

In order to wash at temperatures below 80 00, in particular to achieve a satisfactory bleaching effect in the range of 60 - 40 ° C preferably activator-containing bleaching components are incorporated into the preparations.

Serve as activators for per-compounds which produce H202 in water certain N-acyl, O-acyl compounds that form organic peracids with this H202 as well as carbonic acid or pyrocarbonic acid esters, their activation value for the per compounds (= Titer) is at least 3, preferably at least 4.5.

This activation value is determined in the following way: Solutions, which contain 0.615 g / l NaB02 H202 3 H20 (4 mmol / l) and 2.5 g / l Nal; P207 10 H2O, are added after heating to 60 ° C with 4 mmol / l activator and 5 minutes under Stirring kept at the specified temperature. Then you give 100 ml of this liquid on a mixture of 250 g of ice and 15 ml of glacial acetic acid and titrated immediately after the addition of 0.35 g of potassium iodide with 0.1 N atriuthiosulrate solution and starch as an indicator; the amount of thiosulfate solution consumed in ml is the activation value (= Titer); with 100% activation of the peroxide used, it would be 8.0 ml turn off.

The activators which can be used according to the invention include in particular those N-diacylated and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetyl methylenediamine or ethylenediamine, N, N-dincetylaniline and N, N-diacetyl-p-toluidine or

1,3-diacylated hydantoins, such as the compounds 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionylhydantoin, as well as the compounds tetraacetylglycoluril and tetrapropionylglycoluril.

When the per compounds are activated by the aforementioned N-acyl and O-acyl compounds become carboxylic acids, e.g.

Acetic acid, propionic acid, benzoic acid, free; it is usually recommended add basic salts to bind these carboxylic acids. With effective activators is an activation already at amounts of 0.05 mol of activator per g-atom Detect active oxygen. It is preferred to work with 0.1-1 mol of activator; the However, the amount can also be increased to 2 mol of activator per g atom of active oxygen will.

The active chlorine compounds used as bleaching agents can be more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, in particular in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as pyro- and polyphosphates or can be used on alkali silicates.

If the solid preparations contain monopersulphates and chlorides, then forms active chlorine in aqueous solution.

The organic active chlorine compounds are in particular the N-chlorine compounds in question, in which one or two chlorine atoms are bonded to a nitrogen atom, preferably the third valence of the nitrogen atoms to an electron-withdrawing one Group leads, in particular to a CO or S02 group. These connections include Dichloro and trichlorocyanuric acid or salts thereof, chlorinated alkylguanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.

The detergents can be used as optical brighteners for cotton in particular Derivatives of diaminostilbene disulfonic acid or

contain their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazln-6-yl-amino) -stilbene-2,2'-disulfonic acid are suitable or similarly structured compounds which, instead of the morpholino group, have a Diethanolamino group, a methylamino group or a 2-methoxyethylamino group wear. Brighteners of the 1,3-diaryl-2-pyrazoline type are used as brighteners for polyamide fibers in question, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds which, instead of the sulfamoyl group, e.g. the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group wear. Usable polyamide brighteners are also the substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. Farther are the compounds 1 (2..Benzimidazolyl) -2- (1-hy droxyäthyl-2-benzimidazolyl) ethylene as polyamide brighteners and 1-thyl-3-phenyl-7-diethylamino-carbostyril can be used. As a brightener for polyester and Polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. You can also use brighteners of the substituted 4,4'-distyryldiphenyl type be present; e.g. the connection 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Also mixtures of the aforementioned brighteners can be used.

The enzyme preparations to be used are usually a mixture of enzymes with different effects, e.g. of proteases, carbohydrases, esterases, lipases, Oxidoreductases, catalases, peroxidase, ureases, isomerases, lyases, transferases, Desmolases or nucleases. Those from bacterial strains are of particular interest or enzymes obtained from fungi such as Bacillus subtilis or Streptomyces griseus, in particular Proteases or amylases that oppose alkali, percompounds and anionic surfactants are relatively stable and are still effective at temperatures of up to 70 ° C.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions of the active ingredients or as powder granules or as cold-atomized products in the Trade brought. They often contain sodium sulfate, sodium chloride, Alkali ortho-, pyro or polyphosphates, especially tripolyphosphate. Special ones Value is placed on dust-free preparations; they are obtained in a manner known per se by incorporating oily or pasty nonionics or by granulating with the help of molten salts containing crystalline water in your own crystalline water.

Enzymes can be incorporated for a certain type of dirt are specific, for example proteases or amylases or lipases; preferred one uses combinations of enzymes with different effects, especially combinations from proteases and amylases.

Antimicrobial agents here are bactericidal or bacteriostatic or fungicidal or fungistatic compounds understood. These active ingredients should be water-soluble either as such or in the form of their salts. Both Antimicrobial active substances which can be used according to the invention are mostly involved around phenolic compounds of the halogenated phenol type with 1 - 5 halogen substituents, especially chlorinated phenols; Alkyl, cycloalkyl, aralkyl and phenyl phenols with 1 - 12 carbon atoms in the alkyl radicals and with 1 - 4 halogen substituents, especially chlorine and bromine in the molecule; Alkylene bisphenols, especially through 2 - 6 halogen atoms and optionally substituted lower alkyl or trifluoromethyl groups Derivatives with an alkylene bridge member consisting of 1 to 10 carbon atoms; Hydroxybenzoic acids or their esters and amides, in particular anilides, which are in the benzoic acid and / or aniline radical, in particular through 2 or 3 halogen atoms and / or trifluoromethyl groups can be substituted; o-Phenoxyphenols, by 1 - 7, preferably 2 - 5 Halogen atoms and / or the hydroxyl, cyano, carbomethoxy and carboxyl group or lower alkyl may be substituted; a particularly preferred derivative of o-phenoxyphenol is 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether.

Examples The preparation of the polyvinyloxysuccinic acids according to the invention, their complexing properties and their use in detergents, dishwashing detergents and cleaning agents is illustrated by the following examples.

Example 1 a) Acetaldehyde bis (1,2-dicarbomethoxy-ethyl) acetal In a reaction flask was given 1.5 g of mercury oxide and 7.5 g of a BF3-methanol complex (Molar ratio 1: 1) presented and the mixture heated until about half of the mercury oxide had gone into solution. Thereafter, 394.8 g (2.44 mol) of dimethyl malate were obtained added and at 25 - 30 ° with vigorous stirring slowly acetylene over the surface the mixture passed. The acetylene was rapidly absorbed with evolution of heat. After 4 hours

a total of 27.8 g (1.06 moles) of acetylene had been taken up.

While cooling with ice, first 10 g of solid sodium carbonate and then 25 ml of a saturated Na2CO3 solution were added to the mixture. After adding 500 ml of ether was separated off and the ethereal phase was washed with water and dried and narrowed. The remaining residue was distilled twice in vacuo. It a colorless oil 20 with a boiling point of 165-67 ° / 0.2 mm and a refractive index nD = 1,4483-87 obtained. Gas chromatographic purity: 98%.

b) Vinyloxysuccinic acid dimethyl ester 372.1 g (1.03 mol) of the after a) acetals produced were after the addition of 0.52 g NaHS04 in a distillation apparatus heated with attached Vigreux column in a water jet vacuum. At a sump temperature from 152-180 ° (bath temperature: 180-220 0) distilled in the range from 125-128 0/15 mm 342.6 g of a mixture of dimethyl vinyloxysuccinate and dimethyl malate above. To separate the malic acid ester, water was added to the distillate, the remaining oil separated and dissolved in ether. After washing out several times the ethereal solution was concentrated with water and drying over sodium sulfate and the residue is distilled in vacuo. The product was dated as a colorless oil Boiling point 68 - 70 0 / 0.2 mm and 20 refractive index nD = 1.4422 obtained. Gas chromatographic Purity: 100%.

c) Dimethyl polyvinyloxysuccinate To a solution of 65 g (0.346 mol) of dimethyl vinyloxysuccinate in 200 ml of CH2C12 were at -50 A total of 1.3 ml of BF3 atherate was dripped through a capillary down to -6o °. Under increase Polymerization occurred at the viscosity of the solution.

The mixture was stirred at -50 9 for 2 hours, with further methylene chloride added, the methylene chloride phase washed with water, dried and concentrated. A colorless viscous oil remained, which was reprecipitated from benzene / gasoline. That Product had an average molecular weight MW = 1780 (osmometric determination in benzene).

d) Polyvinyloxysuccinic acid To a solution of 60 g of the according to c) obtained dimethyl ester in 200 ml of methanol was a solution of 40 g (1 mol) NaOH in 200 ml of water and the solution under nitrogen for 5 1/2 hours at 75 - heated to 80 °. Then activated charcoal was added, the mixture was filtered and the solution was poured over a cation exchanger (Lewatit S 100) passed. Part of the eluate was evaporated and the residue is dried in vacuo over P205. The polyvinyloxysuccinic acid thus obtained had the acid number AN = 688 (calculated value: AN - 701).

The remaining eluate was adjusted to pH = 9.5 with dilute sodium hydroxide solution set and evaporated. The sodium salt became the brownish solid product obtained from polyvinyloxysuccinic acid.

1: Copolymers with ethylene, propylene, isobutylene, styrene, methyl vinyl ether, Vinyl acetate, acrylic acid, maleic anhydride are obtained if they are equimolar Amounts with vinyloxysuccinic acid ester in the process stage of example lc) are implemented, and then hydrolyzed and worked up as in Example ld).

Example 2 Determination of the calcium complex binding capacity The determination was carried out at 20 oC and at 95 ° C; the values obtained were with those of sodium triphosphate compared. For this purpose, that amount was used with the 20 ° C method of complexing agents determined to dissolve freshly precipitated calcium carbonate was necessary. With the 95 ° C method, the amount of complexing agent would be determined which just prevented the precipitation of an calcium carbonate precipitate.

From the polyvinyloxysuccinic acid sodium salt prepared according to Example 1 a solution of 10 g / l adjusted to pH 10 was prepared; to the A corresponding solution of sodium triphosphate was used for comparison.

5.5 ml of a 10 g / l soda solution at 20 oC were in a beaker submitted and with stirring 50 ml of a calcium chloride solution corresponding to 56 Od admitted in one shot.

Then 44.5 ml of distilled water (20 ° C.) were added and immediately started dropping the solution of the complexing agent. The end point of the titration was reached after adding 9.4 ml when the solution became clear or only weakly was opaque. The entire titration process was completed within 20 seconds, to avoid aging of the calcium carbonate precipitate.

In the 95 ° C determination 5.5 ml of the soda solution were presented, the distilled water was added, then 50 ml of the calcium chloride solution in a Shot added and immediately afterwards the amount of complexing agent solution added, which was determined in the 20 ° determination. Keep the solution clear from this operation, the value obtained at 20 oC would also be used as the final value for the 95 oC regulation apply. In fact, a precipitate occurred, so that in further Approaches gradually increased amounts of the Complexing agent solution used became. In this way, for the substance according to Example 1, a consumption of 13.5 ml of the 10 g / l solution were determined.

The calcium complex binding capacity is determined by the ouotient of gramions complexed calcium expressed per mole of complexing agent. For the active ingredient of Example 1 was found: Molecular weight 204 at 20 ° C: gram ions Ca / mol = = = 1.1 equivalent weight 9.4. 20 Molecular weight 204 at 95 ° C: gram ions Ca / mol = = = 0.7 equivalent weight 13.9. 20 The corresponding values for sodium triphosphate are at 1.0 (20 00) and 0.7 (95 ° C).

The following examples describe compositions of some washing, Washing auxiliaries, dishwashing detergents and cleaning agents containing polyvinyloxysuccinates according to the invention. The percentages of the components were converted to anhydrous agents, with the exception of the constituents borax and perborate, in which the water of crystallization is specified.

The terms in the examples have the following meanings; salty components are available as sodium salts.

"ABS" means the salt of a product made by condensing straight chain olefins alkylbenzenesulfonic acid obtained with benzene and sulfonation of the alkylbenzene thus formed with 10-15, essentially 11-13 carbon atoms in the alkyl chain.

"Alkanesulfonate" is made up of paraffins with 12-16 carbon atoms sulfonate obtained by sulfoxidation.

"Rs-ester sulfonate" is made from the methyl ester of a hardened tallow fatty acid sulfonate obtained by sulfonation with SO3.

"Olefin sulfonate" is a mixture of olefins with 15-18 carbon atoms Sulphonation with SO3 and hydrolysis of the sulphonation product with alkali Sulfonate, which consists essentially of alkene sulfonate and hydroxyalkane sulfonate, but also contains small amounts of disulfonates.

"KA-Sulrat" is the salt of a sulphated, obtained by reducing coconut fatty acid produced fatty alcohol.

"KA-ÄO-Sulrat" is the salt of the sulfated addition product of 2 moles of ethylene oxide in 1 mole of coconut fatty alcohol.

"Soap" means a fatty acid mixture of 8% by weight of 016, 32% by weight Soap produced C18, 12 wt. 02o and 48 wt. C22 (iodine number 4).

"OA + 10 ÄO", "OA + 5 ÄO", "TA + 17 ÄO" are the addition products of ethylene oxide (Ä0) in technical oleyl alcohol (OA) or tallow alcohol (TA).

"NTA", "EDTA" and "HEDP" are the salts of nitrilotriacetic acid, the Ethylenediaminetetraacetic acid or hydroxyethane diphosphonic acid.

"Perborate" is a product of the approximate composition NaB02 H202 3 3 N O.

"CMC" the salt of carboxymethyl cellulose, degree of substitution 0.7 - 0.8.

"Stilbene brightener" means a compound of the formula 4,4'-bis- (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid, sodium salt.

"Pyrazoline brightener" means a compound of the formula 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline.

As "polyvinyloxysuccinate", one obtained by polymerizing dimethyl vinyloxysuccinate obtained with boron trifluoride etherate and subsequent saponification with sodium hydroxide solution Substance with an average molecular weight of 1800 MW is used.

A "non-surfactant foam inhibitor" was used in the examples Mixture of about 45% of an N, N'-di (alkylamino) chlorotriazine and about 55% of one N, N ', N "-Tri- (alkylamino) -triazines are used. In these triazine derivatives lie the alkyl radicals as a mixture of homologues with 8-18 carbon atoms. With something similar The monochlorotriazine derivative or the trialkylaminotriazine were also successful use.

In the manufacture of powdered preparations, the non-surfactant Foam inhibitor sprayed onto the preparation.

Example 3: Cleaning agent for the metal industry 5.0% by weight ABS, 30.0% by weight, (> polyvinyl oxysuccinate, 30.0% by weight sodium hydroxide, 20.0% by weight Na2O . 3.3 SiO2, 15.0 wt% sodium sulfate.

Example 4: Detergent for the food industry 2.0% by weight ABS, 25.0% by weight polyvinyl oxysuccinate, 48.0% by weight sodium hydroxide, 15.0% by weight Na2O. 3.3 SiO2, 10.0 wt% sodium sulfate.

Example 5: Foam-dampened heavy-duty textile detergent 8.0% by weight ABS, 3.5% by weight soap, 2.5% by weight OA + 10 A0, 40.0% by weight polyvinyl oxysuccinate, 0.5% by weight EDTA, 28.0% by weight perborate, 1.5% by weight magnesium silicate, 1.2% by weight CMC, 0.5% by weight non-surfactant foam inhibitor, 0.5% by weight stilbene brightener, the remainder sodium sulfate and water, dyes and fragrances.

Example 6: High-foaming fine textile detergent 10.0% by weight ABS, 5.0 Wt% KA-Ao-sulfate, 5.0 wt% & Fs-ester sulfonate, 3.0 wt% OA + 10 0, 30.0 % By weight polyvinyl oxysuccinate, 3.0% by weight HEDP, 10.0% by weight Na2CO3, 10.0% by weight NaHCO3, 0.3% by weight stilbene brightener, 0.2% by weight pyrazoline brightener, the remainder sodium sulfate and Water.

Example 7: Soaking and pre-wash detergent 4.0% by weight ABS, 30.0% by weight Polyvinyloxysuccinate, 3.0 wt .-% Na2O 3.3 SiO2, 30.3 wt .-% Na2CO3, 1.0 wt .-% CMC, 2.0% by weight of enzymes, the remainder being sodium sulfate and water.

Example 8: Household cleaning agents for non-textile materials 4.0 wt. OA + 10 EO, 40.0 wt. Polyvinyl oxysuccinate, 15.0 wt. Na5P3010 '6.0 Wt% Na2O. 3.3 SiO2, remainder sodium sulfate and water.

Example 9: Colored detergent 10.0% by weight of olefin sulfonate, 2.0% by weight KA sulfate, 3.0% by weight TA + 14 ÄO, 0.8% by weight non-surfactant foam inhibitor, 30.0% by weight polyvinyl oxysuccinate, 10.0% by weight Na5P3O10 '5.0% by weight NTA, 15.0% by weight Na2CO3, 5.0 wt% Na2O. 3.3 SiO2, 1.5% by weight CMC, the remainder sodium sulfate and water.

Example 10: Disinfecting surface cleaning agent 25.0% by weight a mixture of 50.0% by weight ABS, 45.0% by weight polyvinyl oxysuccinate, 5.0% by weight 2-hydroxy-4,4'-trichlorodiphenyl ether, together with 75.0% by weight of a mixture from 0.2 wt .-% perfume oil, 10.0 wt .-% isopropyl alcohol and 89.8 wt .-% water.

Example 11: Activator-containing bleaching detergent 5.0% by weight Fs-ester sulfonate, 6.0% by weight alkanesulfonate, 4.0% by weight soap, 0.5% by weight HEDP, 0.5 Weight percent non-surfactant foam inhibitor, 20.0 weight percent polyvinyl oxysuccinate, 15.0 Wt% Na2003, 5.0 wt% Na2O. 3.3 SiO2, 15.0% by weight perborate, 1.0% by weight magnesium silicate, 5.0% by weight tetraacetylglycoluril, 0.5% by weight stilbene brightener, 1.2% by weight CMC, remainder Sodium sulfate and water.

Example 12: Dishwashing detergent for machine washing 55.0% by weight Polyvinyloxysuccinate, 42.0 wt. Sodium metasilicate with the composition Na2O 2.75 SiO2, 1.0 wt .-% OA + 5 A0, 2.0 wt .-% potassium dichloroisocyanurate, example 13: Liquid Textile detergent 8.0% by weight ABS, 5.0% by weight OA + 10 AO, 5.0% by weight alkanesulfonate, 3.0% by weight KA-AO sulfate, 3.0% by weight EDTA, 8.0% by weight polyvinyl oxysuccinate, 5.0% by weight Potassium toluenesulfonate, 0.3% by weight 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether, 5.0% by weight Isopropyl alcohol, the rest water, dyes and fragrances.

Claims (10)

Godparents check 1. Polyvinyloxysuccinic acids, consisting essentially of units of the formulas Ia and Ib in which -A- the monomer unit of a polymerizable hydrocarbon, ether, ester or a mono- or dicarboxylic acid and preferably the ethylene, propylene, l, l-dimethylethylene, phenylethylene, methoxyethylene, acetoxyethylene, carboxyethylene or the 1 , 2-Dicarbcxyäthylenrest, where the units of the formulas Ia and Ib can be arranged in any order and n is at least 30 mol% of the copolymer, and the average degree of polymerization is between 3 and 100, preferably between 5 and 50. 2. Polyvinyloxysuccinic acids according to claim 1, characterized in that that they consist entirely of units of the formula Ia. 3. Process for the preparation of the polyvinyloxysuccinic acids according to Claims 1 and 2, characterized in that a vinyloxysuccinic acid ester is used a lower monohydric alcohol, preferably the methyl ester, alone or with a comonomer A, preferably with ethylene, propylene, isobutylene, styrene, methyl vinyl ether, Vinyl acetate, acrylic acid, maleic anhydride, in an inert solvent a temperature from 0 ° C to -100 00, preferably from -30 to -80 00, with catalytic Quantities of a Lewis acid, preferably reacted with boron trifluoride etherate and that obtained polymers saponified after removal of the solvent, and optionally isolated in the form of the alkali salts. 4. The method according to claim 3, characterized in that the Polymerized compound vinyloxysuccinic acid methyl ester. 5 .. Use of the polyvinyloxysuccinic acids according to claim 1 - 4, preferably in the form of their water-soluble salts, in detergents, dishwashing detergents and cleaning agents, which are in solid form, as pastes, dispersions or solutions that have a Have content of complexing agents for alkaline earth metal ions, and those on the water- and / or solvent-free products, characterized by the following composition are: 5 - 95 wt .-% of the polyvinyloxysuccinic acids according to claims 1-4, 95-5 % By weight of other common additives of detergents, dishwashing detergents and cleaning agents, in particular organic or inorganic cleaning action, preferably phosphorus and nitrogen-free substances. 6. Use in cleaning agents, preferably for industrial use Cleaning the surfaces of solid materials with the exception of textiles, according to claim 5, characterized by the following composition: 5 - 30 wt .- polyvinyloxysuccinic acids according to claim 1 - 4, 10 - 95 wt .-% phosphorus-free, cleaning substances from the group of alkali silicates, alkali carbonates and caustic alkalis, O - 10 wt. 4 Surfactants. 7. Use in detergents and cleaning agents, their goat aqueous Solutions have a pH value of at most 11.5, according to claim 5, characterized by the following composition: O - 80, preferably 5 - 40 wt. a surfactant component consisting of anionic and / or zwitterionic and / or nonionic surfactants, 5 to 95, preferably 10 to 80 ow as builder substances Serving polyvinyloxysuccinic acids according to claims 1-4, 95-0, preferably 90 - 20 wt. - Other inorganic and / or organic builder substances and optionally a bleaching component, 0-30, preferably 1-25 wt. - other common ingredients of detergents and cleaning agents. 8. Use in detergents and cleaning agents, preferably for washing of textiles according to claim 7, characterized by the following composition: 5 - 50, preferably 8 - 40% by weight of a surfactant component, consisting essentially from ionic and / or zwitterionic and / or non-chemical surfactants as well optionally from one or more of the following substances: 0-10, preferably 0.5-8% by weight foam stabilizers, 0-10, preferably 0.5-8% by weight non-surfactant Foam inhibitors, 95-5, preferably 92-10% by weight polyvinyloxysuccinic acids according to claim 1 - 4, 0 - 90, preferably 5 - 82 wt .-% inorganic and / or other organic builders and possibly a bleaching component and O - 30, preferably 1-15% by weight of other detergent ingredients, such as dirt carriers, Fabric softeners, antimicrobials, enzymes, brighteners, dyes and fragrances, water. 9. Use in agents according to claim 7 and 8, characterized by the presence of a bleaching component in amounts of 5-40, preferably 7-35 Wt%. 10. Use in agents for machine washing dishes, according to Claim 5, characterized by the following composition: 5-90% by weight polyvinyloxysuccinic acids according to claims 1-4, 95-5 wt. water-soluble alkali silicates, 0-20 wt. alkali hydroxides or alkali carbonates, O - 10 wt. - low foaming nonionic surfactants, O - 25% by weight of other common ingredients in dishwashing detergents, such as active chlorine compounds, Enzymes, complexing agents for heavy metals, dyes and fragrances.